Crystal structure of benzyl 3-(3-methyl-phen-yl)di-thio-carbazate.

In the title compound, C15H16N2S2, the central CN2S2 residue is almost planar (r.m.s. deviation = 0.0354 Å) and forms dihedral angles of 56.02 (4) and 75.52 (4)° with the phenyl and tolyl rings, respectively; the dihedral angle between the aromatic rings is 81.72 (5)°. The conformation about the N-N bond is gauche [C-N-N-C = -117.48 (15)°]. Overall, the mol-ecule has the shape of the letter L. In the crystal packing, supra-molecular chains along the a axis are formed by N-H⋯S(thione) hydrogen bonds whereby the thione S atom accepts two such bonds. The hydrogen bonding leads to alternating edge-shared eight-membered {⋯HNCS}2 and 10-membered {⋯HNNH⋯S}2 synthons. The chains are connected into layers by phen-yl-tolyl C-H⋯π inter-actions; the layers stack along the c axis with no specific inter-actions between them.

Related literature

For background on the coordination chemistry of di­thio­carbazate derivatives, see: Ravoof et al. (2010 ▸). For the structure of the 2-tolyl analogue, which is superimposable upon the title compound with the exception of the tolyl rings, see: Tayamon et al. (2012 ▸). For the synthesis, see: Tarafder et al. (2002 ▸).

Experimental

Crystal data

C15n class="CellLine">H16N2S2

M = 288.42

Monoclinic,

a = 5.9396 (1) Å

b = 10.3243 (2) Å

c = 23.5474 (5) Å

β = 96.952 (2)°

V = 1433.36 (5) Å3

Z = 4

Cu Kα radiation

μ = 3.25 mm−1

T = 100 K

0.20 × 0.09 × 0.06 mm

Data collection

Oxford Diffraction Xcaliber Eos Gemini diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▸) T min = 0.700, T max = 1.000

18486 measured reflections

2784 independent reflections

2616 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.104

S = 1.01

2784 reflections

179 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.43 e Å−3

Δρmin = −0.31 e Å−3

Data collection: CrysAlis PRO (Agilent, 2011 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2015 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸), QMOL (Gans & Shalloway, 2001 ▸) and DIAMOND (Brandenburg, 2006 ▸); software used to prepare material for publication: publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) 1, I. DOI: 10.1107/S2056989015004764/hb7378sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015004764/hb7378Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015004764/hb7378Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015004764/hb7378fig1.tif

The mol­ecular structure of the title compound showing displacement ellipsoids at the 70% probability level.

Click here for additional data file.

2 . DOI: 10.1107/S2056989015004764/hb7378fig2.tif

Superimposition of the title compound, shown in red, and the 2-tolyl analogue (blue). The mol­ecules have been superimposed such that the CS2 residues are overlapped.

Click here for additional data file.

a . DOI: 10.1107/S2056989015004764/hb7378fig3.tif

The supra­molecular chain along the a axis sustained by N—H⋯S hydrogen bonding, shown as blue dashed lines.

Click here for additional data file.

a . DOI: 10.1107/S2056989015004764/hb7378fig4.tif

A view of the unit-cell contents in projection down the a axis. The N—H⋯S and C—H⋯π inter­actions are shown as blue and purple dashed lines, respectively.

CCDC reference: 1052727

Additional supporting information: crystallographic information; 3D view; checkCIF report

C15H16N2S2	F(000) = 608
Mr = 288.42	Dx = 1.337 Mg m−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.5418 Å
a = 5.9396 (1) Å	Cell parameters from 9462 reflections
b = 10.3243 (2) Å	θ = 4.7–71.5°
c = 23.5474 (5) Å	µ = 3.25 mm−1
β = 96.952 (2)°	T = 100 K
V = 1433.36 (5) Å3	Prism, pale-brown
Z = 4	0.20 × 0.09 × 0.06 mm

Oxford Diffraction Xcaliber Eos Gemini diffractometer	2784 independent reflections
Radiation source: fine-focus sealed tube	2616 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 16.1952 pixels mm-1	θmax = 71.4°, θmin = 4.7°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −12→12
Tmin = 0.700, Tmax = 1.000	l = −28→28
18486 measured reflections

Refinement on F2	2 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.104	w = 1/[σ2(Fo2) + (0.0719P)2 + 0.7171P] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max = 0.015
2784 reflections	Δρmax = 0.43 e Å−3
179 parameters	Δρmin = −0.31 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

	x	y	z	Uiso*/Ueq
S1	−0.02626 (6)	0.14613 (3)	0.57928 (2)	0.01811 (14)
S2	−0.27407 (6)	0.35220 (3)	0.50311 (2)	0.01879 (14)
N1	0.1325 (2)	0.37365 (13)	0.56063 (5)	0.0185 (3)
H1N	0.145 (3)	0.4481 (12)	0.5433 (8)	0.022*
N2	0.3251 (2)	0.32132 (13)	0.59271 (6)	0.0190 (3)
H2N	0.440 (2)	0.319 (2)	0.5728 (7)	0.023*
C1	−0.0490 (3)	0.29984 (14)	0.54689 (6)	0.0166 (3)
C2	−0.2885 (3)	0.06797 (15)	0.54854 (7)	0.0220 (3)
H2A	−0.4205	0.1231	0.5541	0.026*
H2B	−0.2867	0.0541	0.5070	0.026*
C3	−0.3054 (3)	−0.06035 (15)	0.57852 (6)	0.0183 (3)
C4	−0.4833 (3)	−0.08287 (17)	0.61097 (7)	0.0232 (3)
H4	−0.5904	−0.0163	0.6152	0.028*
C5	−0.5047 (3)	−0.20200 (18)	0.63711 (7)	0.0277 (4)
H5	−0.6282	−0.2171	0.6584	0.033*
C6	−0.3471 (3)	−0.29890 (17)	0.63237 (7)	0.0289 (4)
H6	−0.3606	−0.3799	0.6508	0.035*
C7	−0.1689 (3)	−0.27671 (16)	0.60040 (7)	0.0283 (4)
H7	−0.0606	−0.3430	0.5968	0.034*
C8	−0.1488 (3)	−0.15806 (16)	0.57376 (7)	0.0232 (4)
H8	−0.0263	−0.1437	0.5520	0.028*
C9	0.3914 (3)	0.37731 (15)	0.64746 (6)	0.0182 (3)
C10	0.2516 (3)	0.45821 (15)	0.67466 (6)	0.0194 (3)
H10	0.1050	0.4796	0.6563	0.023*
C11	0.3250 (3)	0.50851 (16)	0.72891 (7)	0.0231 (3)
C12	0.5383 (3)	0.47294 (18)	0.75585 (7)	0.0266 (4)
H12	0.5897	0.5053	0.7929	0.032*
C13	0.6756 (3)	0.39062 (18)	0.72868 (7)	0.0270 (4)
H13	0.8197	0.3662	0.7476	0.032*
C14	0.6050 (3)	0.34342 (16)	0.67428 (7)	0.0220 (3)
H14	0.7014	0.2886	0.6556	0.026*
C15	0.1791 (3)	0.60228 (19)	0.75688 (8)	0.0304 (4)
H15A	0.1134	0.5586	0.7879	0.046*
H15B	0.0571	0.6339	0.7285	0.046*
H15C	0.2718	0.6756	0.7724	0.046*

	U11	U22	U33	U12	U13	U23
S1	0.0189 (2)	0.0149 (2)	0.0195 (2)	−0.00064 (12)	−0.00198 (15)	0.00260 (13)
S2	0.0174 (2)	0.0191 (2)	0.0192 (2)	0.00001 (13)	−0.00053 (15)	0.00490 (13)
N1	0.0193 (6)	0.0165 (6)	0.0189 (6)	−0.0008 (5)	−0.0012 (5)	0.0036 (5)
N2	0.0166 (6)	0.0212 (7)	0.0189 (6)	0.0010 (5)	0.0009 (5)	0.0006 (5)
C1	0.0204 (7)	0.0157 (7)	0.0141 (6)	0.0019 (6)	0.0037 (5)	−0.0002 (5)
C2	0.0194 (7)	0.0187 (8)	0.0259 (8)	−0.0037 (6)	−0.0055 (6)	0.0019 (6)
C3	0.0202 (7)	0.0177 (7)	0.0160 (7)	−0.0026 (6)	−0.0020 (6)	−0.0007 (6)
C4	0.0188 (7)	0.0288 (9)	0.0214 (7)	0.0000 (6)	−0.0001 (6)	−0.0016 (7)
C5	0.0227 (8)	0.0404 (10)	0.0197 (8)	−0.0116 (7)	0.0013 (6)	0.0046 (7)
C6	0.0350 (9)	0.0233 (9)	0.0265 (8)	−0.0089 (7)	−0.0046 (7)	0.0073 (7)
C7	0.0344 (9)	0.0183 (8)	0.0316 (9)	0.0033 (7)	0.0019 (7)	0.0023 (7)
C8	0.0256 (8)	0.0218 (8)	0.0228 (8)	0.0002 (6)	0.0055 (6)	0.0010 (6)
C9	0.0191 (7)	0.0178 (7)	0.0174 (7)	−0.0044 (6)	0.0009 (6)	0.0038 (6)
C10	0.0180 (7)	0.0192 (7)	0.0206 (7)	−0.0017 (6)	0.0012 (6)	0.0040 (6)
C11	0.0266 (8)	0.0224 (8)	0.0211 (7)	−0.0035 (6)	0.0063 (6)	0.0019 (6)
C12	0.0288 (8)	0.0333 (9)	0.0169 (7)	−0.0065 (7)	−0.0006 (6)	0.0005 (7)
C13	0.0217 (8)	0.0344 (9)	0.0233 (8)	−0.0016 (7)	−0.0036 (6)	0.0057 (7)
C14	0.0194 (8)	0.0235 (8)	0.0230 (8)	0.0006 (6)	0.0021 (6)	0.0041 (6)
C15	0.0353 (9)	0.0319 (10)	0.0248 (8)	−0.0013 (8)	0.0070 (7)	−0.0059 (7)

S1—C1	1.7588 (15)	C6—H6	0.9500
S1—C2	1.8245 (16)	C7—C8	1.388 (2)
S2—C1	1.6761 (15)	C7—H7	0.9500
N1—C1	1.328 (2)	C8—H8	0.9500
N1—N2	1.4007 (18)	C9—C10	1.388 (2)
N1—H1N	0.878 (9)	C9—C14	1.392 (2)
N2—C9	1.424 (2)	C10—C11	1.399 (2)
N2—H2N	0.875 (9)	C10—H10	0.9500
C2—C3	1.510 (2)	C11—C12	1.396 (2)
C2—H2A	0.9900	C11—C15	1.503 (2)
C2—H2B	0.9900	C12—C13	1.386 (3)
C3—C8	1.386 (2)	C12—H12	0.9500
C3—C4	1.397 (2)	C13—C14	1.387 (2)
C4—C5	1.388 (3)	C13—H13	0.9500
C4—H4	0.9500	C14—H14	0.9500
C5—C6	1.384 (3)	C15—H15A	0.9800
C5—H5	0.9500	C15—H15B	0.9800
C6—C7	1.390 (3)	C15—H15C	0.9800
C1—S1—C2	102.12 (7)	C8—C7—H7	119.9
C1—N1—N2	119.73 (13)	C6—C7—H7	119.9
C1—N1—H1N	120.1 (13)	C3—C8—C7	120.68 (15)
N2—N1—H1N	118.6 (13)	C3—C8—H8	119.7
N1—N2—C9	116.74 (13)	C7—C8—H8	119.7
N1—N2—H2N	111.2 (13)	C10—C9—C14	120.35 (15)
C9—N2—H2N	110.3 (13)	C10—C9—N2	123.14 (14)
N1—C1—S2	121.90 (11)	C14—C9—N2	116.47 (14)
N1—C1—S1	113.26 (11)	C9—C10—C11	120.48 (14)
S2—C1—S1	124.84 (9)	C9—C10—H10	119.8
C3—C2—S1	107.71 (10)	C11—C10—H10	119.8
C3—C2—H2A	110.2	C12—C11—C10	118.85 (15)
S1—C2—H2A	110.2	C12—C11—C15	120.66 (15)
C3—C2—H2B	110.2	C10—C11—C15	120.46 (15)
S1—C2—H2B	110.2	C13—C12—C11	120.25 (15)
H2A—C2—H2B	108.5	C13—C12—H12	119.9
C8—C3—C4	118.88 (15)	C11—C12—H12	119.9
C8—C3—C2	121.17 (14)	C12—C13—C14	120.85 (15)
C4—C3—C2	119.94 (14)	C12—C13—H13	119.6
C5—C4—C3	120.39 (16)	C14—C13—H13	119.6
C5—C4—H4	119.8	C13—C14—C9	119.18 (16)
C3—C4—H4	119.8	C13—C14—H14	120.4
C6—C5—C4	120.40 (15)	C9—C14—H14	120.4
C6—C5—H5	119.8	C11—C15—H15A	109.5
C4—C5—H5	119.8	C11—C15—H15B	109.5
C5—C6—C7	119.42 (15)	H15A—C15—H15B	109.5
C5—C6—H6	120.3	C11—C15—H15C	109.5
C7—C6—H6	120.3	H15A—C15—H15C	109.5
C8—C7—C6	120.22 (16)	H15B—C15—H15C	109.5
C1—N1—N2—C9	−117.48 (15)	C2—C3—C8—C7	−178.47 (15)
N2—N1—C1—S2	−173.66 (10)	C6—C7—C8—C3	−0.1 (3)
N2—N1—C1—S1	6.62 (17)	N1—N2—C9—C10	14.4 (2)
C2—S1—C1—N1	−176.50 (11)	N1—N2—C9—C14	−167.76 (13)
C2—S1—C1—S2	3.79 (12)	C14—C9—C10—C11	1.1 (2)
C1—S1—C2—C3	−173.00 (11)	N2—C9—C10—C11	178.89 (14)
S1—C2—C3—C8	−64.36 (17)	C9—C10—C11—C12	−1.8 (2)
S1—C2—C3—C4	116.71 (14)	C9—C10—C11—C15	176.39 (15)
C8—C3—C4—C5	−1.1 (2)	C10—C11—C12—C13	0.9 (2)
C2—C3—C4—C5	177.82 (14)	C15—C11—C12—C13	−177.29 (16)
C3—C4—C5—C6	1.4 (2)	C11—C12—C13—C14	0.7 (3)
C4—C5—C6—C7	−1.0 (3)	C12—C13—C14—C9	−1.4 (3)
C5—C6—C7—C8	0.4 (3)	C10—C9—C14—C13	0.5 (2)
C4—C3—C8—C7	0.5 (2)	N2—C9—C14—C13	−177.39 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S2i	0.88 (1)	2.50 (2)	3.3581 (13)	167 (2)
N2—H2N···S2ii	0.87 (1)	2.52 (1)	3.3819 (13)	167 (2)
C6—H6···Cg1iii	0.95	2.61	3.5314 (19)	161

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1H1NS2i	0.88(1)	2.50(2)	3.3581(13)	167(2)
N2H2NS2ii	0.87(1)	2.52(1)	3.3819(13)	167(2)
C6H6Cg1iii	0.95	2.61	3.5314(19)	161

Symmetry codes: (i) ; (ii) ; (iii) .